Thermoplastic Multi-Layer Golf Ball

ABSTRACT

A thermoplastic multi-layer golf ball has a thermoplastic core center with first flexural modulus and diameter from about 21-29 mm; a thermoplastic core layer radially outward with second flexural modulus; and a thermoplastic cover radially outward with third flexural modulus of up to about 5,000-6000. The second flexural modulus is greater than the third flexural modulus. The core layer and core center specific gravities differ by at least about 0.1 g/cm 3 . The first flexural modulus is up to about 15,000 psi and greater than the second flexural modulus, which is up to about 9700, or the second flexural modulus is up to about 15,000 psi and is greater than the first flexural modulus, which is up to about 9700, with the first thermoplastic material including an ionomer resin and a polyolefin elastomer and having a 10-130 kg compression deformation of at least about 4 mm.

FIELD OF THE INVENTION

The invention concerns multi-layer golf balls in which the layers havedifferent flexural moduli.

BACKGROUND

This section provides information helpful in understanding the inventionbut that is not necessarily prior art.

Golf ball core and cover layers are typically constructed with polymercompositions including, for example, polybutadiene rubber,polyurethanes, polyamides, ionomers, and blends of such polymers.Ionomers, particularly ethylene-based ionomers, are a preferred group ofpolymers for golf ball layers because of their toughness, durability,and wide range of hardness values.

Golf ball compositions comprising highly neutralized acid polymers areknown. For example, U.S. Pat. No. 7,375,151, the entire disclosure ofwhich is incorporated herein by reference, discloses a highly-resilientthermoplastic ionomer resin composition comprising (a) melt-processable,ethylene acid copolymer; (b) aliphatic, mono-functional organic acid orits salt; (c) a thermoplastic resin; (d) a cation source; and (e)optionally, a filler. The ionomer resin may be neutralized to greaterthan 90% of all the acid groups present and remain melt-processable. Thepatent discloses using the highly-resilient thermoplastic composition inone-piece, two-piece, three-piece, and multi-layered golf balls.

Differences in flexural modulus between layers in a ball with a curedrubber core have been described in Loper et al., US Patent ApplicationPublication No. 2012/0129630, for example. Construction of athermoplastic ball, in which all layers are thermoplastic, must providegood performance characteristics to compete with rubber-containing golfballs. While various uses for highly neutralized acid polymers in golfballs have been discovered, there is a need to improve golf ballcharacteristics when using combinations of thermoplastic polymers toprovide golf ball constructions having desirable spin, feel, and CORproperties.

SUMMARY OF THE DISCLOSURE

This section provides a general summary of the disclosure and is notcomprehensive of its full scope or all of the disclosed features.

In one aspect of the disclosed technology, a thermoplastic multi-layergolf ball has a core center with a diameter from about 21 mm to about 29mm and includes a first thermoplastic material having a first flexuralmodulus up to about 15,000 psi, a core layer disposed radially outwardfrom and enclosing the core center, the core layer having a thickness ofat least about 4 mm and including a second thermoplastic material havinga second flexural modulus of up to about 9700 psi, and a cover disposedradially outwardly from the core layer and forming an outer structurallayer of the ball, the cover including a third thermoplastic materialhaving a third flexural modulus of up to about 6,000 psi. The firstflexural modulus is greater than the second flexural modulus, the secondflexural modulus is greater than the third flexural modulus. and thespecific gravities of the core layer and the core center differ by atleast about 0.1 g/cm³.

In the first disclosed aspect, the ball preferably is fullythermoplastic and has no rubber thermoset layer. The ball may have oneor more further core layers. The cover may be a single-layer ormulti-layer cover. In certain embodiments, the second flexural modulusmay be at least about 5,000 psi greater than the third flexural modulus.

In another aspect of the technology, a golf ball has a core center thathas a diameter of from about 21 mm to about 29 mm and includes a firstthermoplastic material that includes an ionomer resin and a polyolefinelastomer and has a 10-130 kg compression deformation of at least about4 mm and a first flexural modulus of up to about 9700 psi; a core layerdisposed radially outward from the core center with a thickness of atleast about 5 mm and including a second thermoplastic material having asecond flexural modulus of up to about 15,000 psi; and a cover disposedradially outward from the core layer that includes a third thermoplasticmaterial having a third flexural modulus of up to about 5,000 psi. Thesecond flexural modulus is at least about 10,000 psi greater than thethird flexural modulus, the second flexural modulus is greater than thefirst flexural modulus, and the specific gravity of the core layer andthe specific gravity of the core center differ by at least about 0.1g/cm3.

Again, the ball preferably is fully thermoplastic and has no rubberthermoset layer. The ball may have one or more further core layers. Thecover may be a single-layer or multi-layer cover.

The golf ball has a multi-layer core including a core center as aninnermost core part and one or more “core layers” outward from andenclosing the center. A “core layer” for this invention is any golf balllayer lying between the center and the cover of the golf ball. Indescribing this invention, a “cover” is the outermost structural golfball layer of the ball or, for two cover layers, each “cover layer” isone of the two outermost structural golf ball layers. Coating layers(whether paint layers or clear coating layers) are not considered to bestructural layers.

Flexural modulus is measured according to ASTM D790. Specific gravity ismeasured according to ASTM D792. “Compression deformation” is thedeformation amount in millimeters under a compressive load of 130 kgminus the deformation amount in millimeters under a compressive load of10 kg. The amount of deformation of the ball under a force of 10 kg ismeasured, then the force is increased to 130 kg and the amount ofdeformation under the new force of 130 kg is measured. The deformationamount at 10 kg is subtracted from the deformation amount at 130 kg togive the 10-130 kg compression deformation, which is reported inmillimeters.

“A,” “an,” “the,” “at least one,” and “one or more” are usedinterchangeably to indicate that at least one of the item is present;the indefinite articles indicate a plurality of such items may bepresent unless the context clearly indicates otherwise. All numericalvalues of parameters (e.g., of quantities or conditions) in thisspecification, including the appended claims, are to be understood asbeing modified in all instances by the term “about” whether or not“about” actually appears before the numerical value. “About” indicatesthat the stated numerical value allows some slight imprecision (withsome approach to exactness in the value; approximately or reasonablyclose to the value; nearly). If the imprecision provided by “about” isnot otherwise understood in the art with this ordinary meaning, then“about” as used herein indicates at least variations that may arise fromordinary methods of measuring and using such parameters. In addition,disclosure of ranges includes disclosure of all values and furtherdivided ranges within the entire range. Each value within a range andthe endpoints of a range are hereby all disclosed as separateembodiments. In this description of the invention, for convenience,“polymer” and “resin” are used interchangeably to encompass resins,oligomers, and polymers. The terms “comprises,” “comprising,”“including,” and “having,” are inclusive and therefore specify thepresence of stated items, but do not preclude the presence of otheritems. As used in this specification, the term “or” includes any and allcombinations of one or more of the listed items. When the terms first,second, third, etc. are used to differentiate various items from eachother, these designations are merely for convenience and do not limitthe items.

It should be understood that the description and specific examples areintended for purposes of illustration only and are not intended to limitthe scope of the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE is a partial cross-sectional view of an embodiment of amulti-layer golf ball that illustrates some aspects of the disclosedtechnology. The parts of the FIGURE are not necessarily to scale.

DETAILED DESCRIPTION

A detailed description of exemplary, nonlimiting embodiments follows.

As shown in the FIGURE, a multi-layer golf ball 100 has a core center110, a core layer 120 that is radially outward from the core center 110,and a cover 130 that forms the outermost layer of the golf ball 100.Each of the core center, the core layer, and the cover includes athermoplastic material.

The disclosed golf ball has a multi-layer core that includes at least acore center including a first thermoplastic material and a core layerradially outward from the core center including a second thermoplasticmaterial. The ball has a cover including a third thermoplastic material.

Each of the first, second, and third thermoplastic materials may includeat least one thermoplastic elastomer. Each of the first, second, andthird thermoplastic materials may also include one or morenon-elastomeric polymers, plasticizers, fillers, and customaryadditives.

The second thermoplastic material's flexural modulus is greater than thethird thermoplastic material's flexural modulus, preferably by at leastabout 2000 psi, more preferably at least about 3000 psi, and still morepreferably at least about 4000 psi or at least about 5000 psi. Thesecond thermoplastic material's flexural modulus may be greater than thethird thermoplastic material's flexural modulus by from about 2000 psior from about 3000 psi up to about 4000 psi or up to about 5000 psi orup to about 6000 psi or up to about 7000 psi or up to about 8000 psi orup to about 9000 psi. In other embodiments, the second thermoplasticmaterial's flexural modulus may be greater than the third thermoplasticmaterial's flexural modulus by from about 4000 psi or from about 5000psi up to about . up to about 6000 psi or up to about 7000 psi or up toabout 8000 psi or up to about 9000 psi or up to about 10,000 psi or upto about 11,000 psi or up to about 12,000 psi or up to about 13,000 psior up to about 14,000 psi. The third material's flexural modulus is upto about 6000 psi, preferably up to about 5000 psi, more preferably upto about 4000 psi or up to about 3000 psi or up to about 2000 psi or upto about 1500 psi or up to about 1000 psi. In various embodiments, thethird material's flexural modulus may be from about 500 psi or fromabout 700 psi or from about 1000 psi up to about 6000 psi, preferably upto about 5000 psi, more preferably up to about 4000 psi or up to about3000 psi or up to about 2000 psi or up to about 1500 psi or may be fromabout 1500 psi or from about 2000 psi up to about 6000 psi, preferablyup to about 5000 psi, more preferably up to about 4000 psi or up toabout 3000 psi. The specific gravities of the core center and the corelayer differ by at least about 0.1 g/cm³.

In the first disclosed aspect, the first thermoplastic material'sflexural modulus is up to about 15,000 psi, preferably up to about12,000 psi, and is greater than the second thermoplastic material'sflexural modulus, which is up to about 9700 psi, preferably up to about8000 psi. In the first disclosed aspect, the first thermoplasticmaterial's flexural modulus may be from about 8000 psi or from about9000 psi or from about 10,000 psi up to about 11,000 psi or up to about12,000 psi or up to about 13,000 psi or up to about 14,000 psi or up toabout 15,000 psi, while the second thermoplastic material's flexuralmodulus may be from about 4000 psi or from about 4500 psi or from about5000 psi up to about 6000 psi or up to about 7000 psi or up to about8000 psi or up to about 9000 psi or up to about 9700 psi. In a seconddisclosed aspect this relationship is reversed, with the secondthermoplastic material's flexural modulus being up to about 15,000 psi,preferably up to about 12,000 psi, and being greater than the firstthermoplastic material's flexural modulus, which is up to about 9700psi, preferably up to about 8000 psi. In the second disclosed aspect,the second thermoplastic material's flexural modulus may be from about8000 psi or from about 9000 psi or from about 10,000 psi up to about11,000 psi or up to about 12,000 psi or up to about 13,000 psi or up toabout 14,000 psi or up to about 15,000 psi, while the firstthermoplastic material's flexural modulus may be from about 4000 psi orfrom about 4500 psi or from about 5000 psi up to about 6000 psi or up toabout 7000 psi or up to about 8000 psi or up to about 9000 psi or up toabout 9700 psi. Also in the second disclosed embodiment, the secondthermoplastic material's flexural modulus may be at least about 10,000psi greater than the third thermoplastic material's flexural modulus,from example from about 10,000 psi to about 12,000 psi or to about13,000 psi greater than the third thermoplastic material's flexuralmodulus.

The flexural moduli of the first, second, and third thermoplasticmaterials depend on a combination of factors, including the nature andamount of thermoplastic elastomers in the thermoplastic materials, thepresence, nature, and amount of other polymeric materials, and thepresence, nature, and amount of fillers. In general, fillers increasethe flexural modulus of a thermoplastic material. The polymers and thetype and amount of any filler of each of the first, second, and thirdthermoplastic materials are selected and apportioned so that theflexural moduli have the desired relationship. In preferred embodiments,the golf ball is free from any thermoset rubber layer or other thermosetlayer.

The core may have one or more further core layers. In certainembodiments, the golf ball includes a second core layer between the corelayer and the cover. The second core layer includes a fourththermoplastic material with flexural modulus greater than the flexuralmodulus of the second thermoplastic material of the core layer.

The first, second, and third thermoplastic materials generally includeat least one thermoplastic elastomer. Nonlimiting examples of suitablethermoplastic elastomers that can be used in making the golf ball coreand cover include metal cation ionomers of addition copolymers (“ionomerresins”), metallocene-catalyzed block copolymers of ethylene andα-olefins having 4 to about 8 carbon atoms, thermoplastic polyamideelastomers (e.g., polyether block polyamides), thermoplastic polyesterelastomers, thermoplastic styrene block copolymer elastomers such aspoly(styrene-butadiene-styrene),poly(styrene-ethylene-co-butylene-styrene), andpoly(styrene-isoprene-styrene), thermoplastic polyurethane elastomers,thermoplastic polyurea elastomers, and dynamic vulcanizates of rubbersin these thermoplastic elastomers and in other thermoplastic matrixpolymers.

Ionomer resins, which are metal cation ionomers of addition copolymersof ethylenically unsaturated acids, are preferably alpha-olefin,particularly ethylene, copolymers with C₃ to C₈ α,β-ethylenicallyunsaturated carboxylic acids, particularly acrylic or methacrylic acid.The copolymers may also contain a softening monomer such as an alkylacrylate or methacrylate, for example a C₁ to C₈ alkyl acrylate ormethacrylate ester. The α,β-ethylenically unsaturated carboxylic acidmonomer may be from about 4 weight percent or about 6 weight percent orabout 8 weight percent up to about 20 weight percent or up to about 35weight percent of the copolymer, and the softening monomer, whenpresent, is preferably present in a finite amount, preferably at leastabout 5 weight percent or at least about 11 weight percent, up to about23 weight percent or up to about 25 weight percent or up to about 50weight percent of the copolymer.

Nonlimiting specific examples of acid-containing ethylene copolymersinclude copolymers of ethylene/acrylic acid/n-butyl acrylate,ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylicacid/isobutyl acrylate, ethylene/acrylic acid/isobutyl acrylate,ethylene/methacrylic acid/n-butyl methacrylate, ethylene/acrylicacid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate,ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylicacid/methyl methacrylate, and ethylene/acrylic acid/n-butylmethacrylate. Preferred acid-containing ethylene copolymers includecopolymers of ethylene/methacrylic acid/n-butyl acrylate,ethylene/acrylic acid/n-butyl acrylate, ethylene/methacrylic acid/methylacrylate, ethylene/acrylic acid/ethyl acrylate, ethylene/methacrylicacid/ethyl acrylate, and ethylene/acrylic acid/methyl acrylate. Invarious embodiments the most preferred acid-containing ethylenecopolymers include ethylene/(meth)acrylic acid/n-butyl acrylate,ethylene/(meth)acrylic acid/ethyl acrylate, and ethylene/(meth)acrylicacid/methyl acrylate copolymers.

The ionomer resin may be a high acid ionomer resin. In general, ionomersprepared by neutralizing acid copolymers including at least about 16weight % of copolymerized acid residues based on the total weight of theunneutralized ethylene acid copolymer are considered “high acid”ionomers. In these high modulus ionomers, the acid monomer, particularlyacrylic or methacrylic acid, is present in about 16 to about 35 weight%. In various embodiments, the copolymerized carboxylic acid may be fromabout 16 weight %, or about 17 weight % or about 18.5 weight % or about20 weight % up to about 21.5 weight % or up to about 25 weight % or upto about 30 weight % or up to about 35 weight % of the unneutralizedcopolymer. A high acid ionomer may be combined with a “low acid” ionomerin which the copolymerized carboxylic acid is less than 16 weight % ofthe unneutralized copolymer.

The acid moiety in the ethylene-acid copolymer is neutralized by anymetal cation. Suitable preferred cations include lithium, sodium,potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum, or acombination of these cations; in various embodiments alkali metal,alkaline earth metal, or zinc cations are particularly preferred. Invarious embodiments, the acid groups of the ionomer may be neutralizedfrom about 10% or from about 20% or from about 30% or from about 40% toabout 60% or to about 70% or to about 75% or to about 80% or to about90%.

A sufficiently high molecular weight, monomeric organic acid or salt ofsuch an organic acid may be added to the acid copolymer or ionomer sothat the acid copolymer or ionomer can be neutralized, without losingprocessability, to a level above the level that would cause the ionomeralone to become non-melt-processable. The high-molecular weight,monomeric organic acid its salt may be added to the ethylene-unsaturatedacid copolymers before they are neutralized or after they are optionallypartially neutralized to a level between about 1 and about 100%,provided that the level of neutralization is such that the resultingionomer remains melt-processable. In generally, when the high-molecularweight, monomeric organic acid is included the acid groups of thecopolymer may be neutralized from at least about 40 to about 100%,preferably from at least about 90% to about 100%, and most preferably100% without losing processability. Such high neutralization,particularly to levels greater than 70%, greater than 80%, greater than90%, greater than 95%, or most preferably 100%, without loss ofprocessability can be done by (a) melt-blending theethylene-α,β-ethylenically unsaturated carboxylic acid copolymer or amelt-processable salt of the copolymer with an organic acid or a salt oforganic acid, and (b) adding a sufficient amount of a cation source upto 110% of the amount needed to neutralize the total acid in thecopolymer or ionomer and organic acid or salt to the desired level toincrease the level of neutralization of all the acid moieties in themixture preferably to greater than 90%, preferably greater than 95%, orpreferably to 100%. To obtain 100% neutralization, it is preferred toadd a slight excess of up to 110% of cation source over the amountstoichiometrically required to obtain the 100% neutralization.

The high molecular weight, monomeric saturated or unsaturated acid mayhave from 8 or 12 or 18 carbon atoms to 36 carbon atoms or to less than36 carbon atoms. Nonlimiting suitable examples of the high-molecularweight, monomeric saturated or unsaturated organic acids includestearic, behenic, erucic, oleic, and linoleic acids and their salts,particularly the barium, lithium, sodium, zinc, bismuth, chromium,cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, orcalcium salts of these fatty acids. These may be used in combinations.

Thermoplastic polyolefin elastomers may also be used in thethermoplastic materials of the golf ball. These aremetallocene-catalyzed block copolymers of ethylene and α-olefins having4 to about 8 carbon atoms that are prepared by single-site metallocenecatalysis, for example in a high pressure process in the presence of acatalyst system comprising a cyclopentadienyl-transition metal compoundand an alumoxane. Nonlimiting examples of the α-olefin softeningcomonomers include hexane-1 or octene-1; octene-1 is a preferredcomonomer to use. These materials are commercially available, forexample, from ExxonMobil under the tradename Exact™ and from the DowChemical Company under the tradename Engage™.

In various embodiments, the thermoplastic material includes acombination of a metal ionomer of a copolymer of ethylene and at leastone of acrylic acid and methacrylic acid, a metallocene-catalyzedcopolymer of ethylene and an α-olefin having 4 to about 8 carbon atoms,and a metal salt of an unsaturated fatty acid. This material may beprepared as described in Statz et al., U.S. Pat. No. 7,375,151 or asdescribed in Kennedy, “Process for Making Thermoplastic Golf BallMaterial and Golf Ball with Thermoplastic Material, U.S. patentapplication Ser. No. 13/825112, filed 15 Mar. 2013, the entire contentsof both being incorporated herein by reference. The thermoplasticmaterial having a flexural modulus of up to about 9700 psi (which in thefirst disclosed aspect is the second thermoplastic material but in thesecond disclosed aspect is the first thermoplastic material) may includean ionomer resin and a polyolefin elastomer and may have a 10-130 kgcompression deformation of from about 4 mm to about 8 mm, preferablyfrom about 4 mm to about 6 mm.

Suitable thermoplastic styrene block copolymer elastomers that may beused in the thermoplastic materials of the golf ball includepoly(styrene-butadiene-styrene),poly(styrene-ethylene-co-butylene-styrene),poly(styrene-isoprene-styrene), and poly(styrene-ethylene-co-propylene)copolymers. These styrenic block copolymers may be prepared by livinganionic polymerization with sequential addition of styrene and the dieneforming the soft block, for example using butyl lithium as initiator.Thermoplastic styrene block copolymer elastomers are commerciallyavailable, for example, under the trademark Kraton™ sold by KratonPolymers U.S. LLC, Houston, Tex. Other such elastomers may be made asblock copolymers by using other polymerizable, hard, non-rubber monomersin place of the styrene, including meth(acrylate) esters such as methylmethacrylate and cyclohexyl methacrylate, and other vinyl arylenes, suchas alkyl styrenes.

Thermoplastic polyurethane elastomers such as thermoplasticpolyester-polyurethanes, polyether-polyurethanes, andpolycarbonate-polyurethanes may be used in the thermoplastic materials,particularly in the third thermoplastic material for the cover. Thethermoplastic polyurethane elastomers include polyurethanes polymerizedusing as polymeric diol reactants polyethers and polyesters includingpolycaprolactone polyesters. These polymeric diol-based polyurethanesare prepared by reaction of the polymeric diol (polyester diol,polyether diol, polycaprolactone diol, polytetrahydrofuran diol, orpolycarbonate diol), one or more polyisocyanates, and, optionally, oneor more chain extension compounds. Chain extension compounds, as theterm is being used, are compounds having two or more functional groupsreactive with isocyanate groups, such as the diols, amino alcohols, anddiamines. Preferably the polymeric diol-based polyurethane issubstantially linear (i.e., substantially all of the reactants aredifunctional).

Diisocyanates used in making the polyurethane elastomers may be aromaticor aliphatic. Useful diisocyanate compounds used to preparethermoplastic polyurethanes include, without limitation, isophoronediisocyanate (IPDI), methylene bis-4-cyclohexyl isocyanate (H₁₂MDI),cyclohexyl diisocyanate (CHDI), m-tetramethyl xylene diisocyanate(m-TMXDI), p-tetramethyl xylene diisocyanate (p-TMXDI), 4,4′-methylenediphenyl diisocyanate (MDI, also known as 4,4′-diphenylmethanediisocyanate), 2,4- or 2,6-toluene diisocyanate (TDI), ethylenediisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane,1,6-diisocyanatohexane (hexamethylene diisocyanate or HDI), 1,4-butylenediisocyanate, lysine diisocyanate, meta-xylylenediioscyanate andpara-xylylenediisocyanate (XDI), 4-chloro-1,3-phenylene diisocyanate,1,5-tetrahydro-naphthalene diisocyanate, 4,4′-dibenzyl diisocyanate, andcombinations of these. Nonlimiting examples of higher-functionalitypolyisocyanates that may be used in limited amounts to produce branchedthermoplastic polyurethanes (optionally along with monofunctionalalcohols or monofunctional isocyanates) include 1,2,4-benzenetriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecanetriisocyanate, bicycloheptane triisocyanate, triphenylmethane-4,4′,4″-triisocyanate, isocyanurates of diisocyanates, biurets ofdiisocyanates, allophanates of diisocyanates, and the like.

Nonlimiting examples of suitable diols that may be used as extendersinclude ethylene glycol and lower oligomers of ethylene glycol includingdiethylene glycol, triethylene glycol, and tetraethylene glycol;propylene glycol and lower oligomers of propylene glycol includingdipropylene glycol, tripropylene glycol, and tetrapropylene glycol;cyclohexanedimethanol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol,1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,3-propanediol,butylene glycol, neopentyl glycol, dihydroxyalkylated aromatic compoundssuch as the bis (2-hydroxyethyl) ethers of hydroquinone and resorcinol;p-xylene-α,α′-diol; the bis (2-hydroxyethyl) ether ofp-xylene-α,α′-diol; m-xylene-α,α′-diol, and combinations of these. Otheractive hydrogen-containing chain extenders that contain at least twoactive hydrogen groups may be used, for example, dithiols, diamines, orcompounds having a mixture of hydroxyl, thiol, and amine groups, such asalkanolamines, aminoalkyl mercaptans, and hydroxyalkyl mercaptans, amongothers. Suitable diamine extenders include, without limitation, ethylenediamine, diethylene triamine, triethylene tetraamine, and combinationsof these. Other typical chain extenders are amino alcohols such asethanolamine, propanolamine, butanolamine, and combinations of these.The molecular weights of the chain extenders preferably range from about60 to about 400. Alcohols and amines are preferred.

In addition to difunctional extenders, a small amount of a trifunctionalextender such as trimethylolpropane, 1,2,6-hexanetriol and glycerol, ormonofunctional active hydrogen compounds such as butanol ordimethylamine, may also be included. The amount of trifunctionalextender or monofunctional compound employed may be, for example, 5.0equivalent percent or less based on the total weight of the reactionproduct and active hydrogen containing groups used.

The polyester diols used in forming a thermoplastic polyurethaneelastomer are in general prepared by the condensation polymerization ofone or more polyacid compounds and one or more polyol compounds.Preferably, the polyacid compounds and polyol compounds aredi-functional, i.e., diacid compounds and diols are used to preparesubstantially linear polyester diols, although minor amounts ofmono-functional, tri-functional, and higher functionality materials canbe included to provide a slightly branched, but uncrosslinked polyesterpolyol component. Suitable dicarboxylic acids include, withoutlimitation, glutaric acid, succinic acid, malonic acid, oxalic acid,phthalic acid, isophthalic acid, hexahydrophthalic acid, adipic acid,maleic acid, suberic acid, azelaic acid, dodecanedioic acid, theiranhydrides and polymerizable esters (e.g., methyl esters) and acidhalides (e.g., acid chlorides), and mixtures of these. Suitable polyolsinclude those already mentioned, especially the diols. Typical catalystsfor the esterification polymerization are protonic acids, Lewis acids,titanium alkoxides, and dialkyltin oxides.

A polymeric polyether or polycaprolactone diol reactant for preparingthermoplastic polyurethane elastomers may be obtained by reacting a diolinitiator, e.g., 1,3-propanediol or ethylene or propylene glycol, with alactone or alkylene oxide chain-extension reagent. Lactones that can bering opened by an active hydrogen are well-known in the art. Examples ofsuitable lactones include, without limitation, ε-caprolactone,γ-caprolactone, β-butyrolactone, β-propriolactone, γ-butyrolactone,α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone,δ-valerolactone, γ-decanolactone, δ-decanolactone, γ-nonanoic lactone,γ-octanoic lactone, and combinations of these. In one preferredembodiment, the lactone is ε-caprolactone. Useful catalysts includethose mentioned above for polyester synthesis. Alternatively, thereaction can be initiated by forming a sodium salt of the hydroxyl groupon the molecules that will react with the lactone ring. In otherembodiments, a diol initiator may be reacted with an oxirane-containingcompound or cyclic ether to produce a polyether diol to be used in thepolyurethane elastomer polymerization. Alkylene oxide polymer segmentsinclude, without limitation, the polymerization products of ethyleneoxide, propylene oxide, 1,2-cyclohexene oxide, 1-butene oxide, 2-buteneoxide, 1-hexene oxide, tert-butylethylene oxide, phenyl glycidyl ether,1-decene oxide, isobutylene oxide, cyclopentene oxide, 1-pentene oxide,and combinations of these. The oxirane- or cyclic ether-containingcompound is preferably selected from ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, and combinations of these. The alkyleneoxide polymerization is typically base-catalyzed. The polymerization maybe carried out, for example, by charging the hydroxyl-functionalinitiator compound and a catalytic amount of caustic, such as potassiumhydroxide, sodium methoxide, or potassium tert-butoxide, and adding thealkylene oxide at a sufficient rate to keep the monomer available forreaction. Two or more different alkylene oxide monomers may be randomlycopolymerized by coincidental addition or polymerized in blocks bysequential addition. Homopolymers or copolymers of ethylene oxide orpropylene oxide are preferred. Tetrahydrofuran may be polymerized by acationic ring-opening reaction using such counterions as SbF₆ ⁻, AsF₆ ⁻,PF₆ ⁻, SbCl₆ ⁻, BF₄ ⁻, CF₃SO₃ ⁻, FSO₃ ⁻, and ClO₄ ⁻. Initiation is byformation of a tertiary oxonium ion. The polytetrahydrofuran segment canbe prepared as a “living polymer” and terminated by reaction with thehydroxyl group of a diol such as any of those mentioned above.Polytetrahydrofuran is also known as polytetramethylene ether glycol(PTMEG).

Aliphatic polycarbonate diols that may be used in making a thermoplasticpolyurethane elastomer may be prepared by the reaction of diols withdialkyl carbonates (such as diethyl carbonate), diphenyl carbonate, ordioxolanones (such as cyclic carbonates having five- and six-memberrings) in the presence of catalysts like alkali metal, tin catalysts, ortitanium compounds. Useful diols include, without limitation, any ofthose already mentioned. Aromatic polycarbonates are usually preparedfrom reaction of bisphenols, e.g., bisphenol A, with phosgene ordiphenyl carbonate.

In various embodiments, the polymeric diol preferably has a weightaverage molecular weight of at least about 500, more preferably at leastabout 1000, and even more preferably at least about 1800 and a weightaverage molecular weight of up to about 10,000, but polymeric diolshaving weight average molecular weights of up to about 5000, especiallyup to about 4000, may also be preferred. The polymeric dioladvantageously has a weight average molecular weight in the range fromabout 500 to about 10,000, preferably from about 1000 to about 5000, andmore preferably from about 1500 to about 4000. The weight averagemolecular weights may be determined by ASTM D4274.

The reaction of the polyisocyanate, polymeric diol, and diol or otherchain extension agent is typically carried out at an elevatedtemperature in the presence of a catalyst. Typical catalysts for thisreaction include organotin catalysts such as stannous octoate, dibutyltin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, tertiaryamines, zinc salts, and manganese salts. Generally, for elastomericpolyurethanes, the ratio of polymeric diol, such as polyester diol, toextender can be varied within a relatively wide range depending largelyon the desired flexural modulus of the final polyurethane elastomer. Forexample, the equivalent proportion of polyester diol to extender may bewithin the range of 1:0 to 1:12 and, more preferably, from 1:1 to 1:8.Preferably, the diisocyanate(s) employed are proportioned such that theoverall ratio of equivalents of isocyanate to equivalents of activehydrogen containing materials is within the range of 1:1 to 1:1.05, andmore preferably, 1:1 to 1:1.02. The polymeric diol segments typicallyare from about 35% to about 65% by weight of the polyurethane polymer,and preferably from about 35% to about 50% by weight of the polyurethanepolymer.

Suitable thermoplastic polyurea elastomers may be prepared by reactionof one or more polymeric diamines or polyols with one or more of thepolyisocyanates already mentioned and one or more diamine extenders.Nonlimiting examples of suitable diamine extenders include ethylenediamine, 1,3-propylene diamine, 2-methyl-pentamethylene diamine,hexamethylene diamine, 2,2,4- and 2,4,4-trimethyl-1,6-hexane diamine,imino-bis(propylamine), imido-bis(propylamine),N-(3-aminopropyl)-N-methyl-1,3-propanediamine),1,4-bis(3-aminopropoxy)butane, diethyleneglycol-di(aminopropyl)ether),1-methyl-2,6-diamino-cyclohexane, 1,4-diamino-cyclohexane, 1,3- or1,4-bis(methylamino)-cyclohexane, isophorone diamine, 1,2- or1,4-bis(sec-butylamino)-cyclohexane, N,N′-diisopropyl-isophoronediamine, 4,4′-diamino-dicyclohexylmethane,3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane,N,N′-dialkylamino-dicyclohexylmethane, and3,3′-diethyl-5,5′-dimethyl-4,4′-diamino-dicyclohexylmethane. Polymericdiamines include polyoxyethylene diamines, polyoxypropylene diamines,poly(oxyethylene-oxypropylene) diamines, and poly(tetramethylene ether)diamines The amine- and hydroxyl-functional extenders already mentionedmay be used as well. Generally, as before, trifunctional reactants arelimited and may be used in conjunction with monofunctional reactants toprevent crosslinking.

Suitable thermoplastic polyamide elastomers may be obtained by: (1)polycondensation of (a) a dicarboxylic acid, such as oxalic acid, adipicacid, sebacic acid, terephthalic acid, isophthalic acid,1,4-cyclohexanedicarboxylic acid, or any of the other dicarboxylic acidsalready mentioned with (b) a diamine, such as ethylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ordecamethylenediamine, 1,4-cyclohexanediamine, m-xylylenediamine, or anyof the other diamines already mentioned; (2) a ring-openingpolymerization of a cyclic lactam, such as ε-caprolactam orω-laurolactam; (3) polycondensation of an aminocarboxylic acid, such as6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, or12-aminododecanoic acid; or (4) copolymerization of a cyclic lactam witha dicarboxylic acid and a diamine to prepare a carboxylicacid-functional polyamide block, followed by reaction with a polymericether diol (polyoxyalkylene glycol) such as any of those alreadymentioned. Polymerization may be carried out, for example, attemperatures of from about 180° C. to about 300° C. Specific examples ofsuitable polyamide block copolymers include NYLON 6, NYLON 66, NYLON610, NYLON 11, NYLON 12, copolymerized NYLON MXD6, and NYLON 46 basedelastomers. Thermoplastic poly(ether amide) block copolymer elastomers(PEBA) are commercially available under the trademark Pebax® fromArkema.

Thermoplastic polyester elastomers have blocks of monomer units with lowchain length that form the crystalline regions and blocks of softeningsegments with monomer units having relatively higher chain lengths.Thermoplastic polyester elastomers are commercially available under thetrademark Hytrel® from DuPont.

The thermoplastic materials of the golf ball core and cover may includecombinations of thermoplastic elastomers. In one embodiment, athermoplastic material includes a combination of a metal ionomer of acopolymer of ethylene and at least one of acrylic acid and methacrylicacid, a metallocene-catalyzed copolymer of ethylene and an α-olefinhaving 4 to about 8 carbon atoms, and a metal salt of an unsaturatedfatty acid. This material may be prepared as described in Statz et al.,U.S. Pat. No. 7,375,151 or as described in Kennedy, “Process for MakingThermoplastic Golf Ball Material and Golf Ball with ThermoplasticMaterial, U.S. patent application Ser. No. 13,825112, filed 15 Mar.2013, the entire contents of both being incorporated herein byreference.

In various embodiments, the first thermoplastic material includes anionomer resin and a polyolefin elastomer. First thermoplastic materialswith this combination may have a 10-130 kg compression deformation of atleast about 4 mm, preferably at least about 6 mm.

In various embodiments, at least one of the first thermoplasticmaterial, the second thermoplastic material, and the third thermoplasticmaterial includes a polymer selected from ionomer resins, polyamideelastomers, polyurethane elastomers, thermoplastic polyester elastomers,and combinations of these.

The first and second thermoplastic materials may include other polymers.In one example, the first or second thermoplastic material may includedispersed domains of cured rubbers, which may be incorporated in athermoplastic elastomer matrix via dynamic vulcanization of rubbers inany of these thermoplastic elastomers or in other thermoplasticpolymers. One such composition is described in Voorheis et al, U.S. Pat.No. 7,148,279, which is incorporated herein by reference. In variousembodiments, the first thermoplastic material may include athermoplastic dynamic vulcanizate of a rubber in a non-elastomericmatrix resin such as polypropylene. Thermoplastic vulcanizatescommercially available from ExxonMobil under the tradename Santoprene™are believed to be vulcanized domains of EPDM in polypropylene.

Depending on the elastomer selected for each thermoplastic material, oneor more plasticizers may be incorporated. One example of such aplasticizer is the high molecular weight, monomeric organic acid or itssalt that may be incorporated, for example, with an ionomer polymer asalready described, including metal stearates such as zinc stearate,calcium stearate, barium stearate, lithium stearate and magnesiumstearate. For most thermoplastic elastomers, the percentage ofhard-to-soft segments is adjusted if lower hardness is desired ratherthan by adding a plasticizer.

The flexural modulus of a thermoplastic material may be increased byincluding a filler. Various fillers may be included, and the filler mayalso be selected to modify the specific gravity, hardness, or otherproperties of the thermoplastic material. Nonlimiting examples ofsuitable fillers include clay, talc, asbestos, graphite, glass, mica,calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide,silicates, diatomaceous earth, carbonates (such as calcium carbonate,magnesium carbonate and the like), metals (such as titanium, tungsten,aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron,bronze, cobalt, beryllium and alloys of these), metal oxides (such aszinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide,zirconium oxide and the like), particulate synthetic plastics (such ashigh molecular weight polyethylene, polystyrene, polyethylene ionomericresins and the like), particulate carbonaceous materials (such as carbonblack, natural bitumen and the like), as well as cotton flock, celluloseflock and/or leather fiber. Nonlimiting examples of heavy-weight fillersthat may be used to increase specific gravity include titanium,tungsten, aluminum, bismuth, nickel, molybdenum, iron, steel, lead,copper, brass, boron, boron carbide whiskers, bronze, cobalt, beryllium,zinc, tin, and metal oxides (such as zinc oxide, iron oxide, aluminumoxide, titanium oxide, magnesium oxide, zirconium oxide). Nonlimitingexamples of light-weight fillers that may be used to decrease specificgravity include particulate plastics, glass, ceramics, and hollowspheres, regrinds, or foams of these. Fillers that may be used in thecore center and core layers of a golf ball are typically in a finelydivided form.

Various heavy-weight or light-weight fillers may be included in thedifferent thermoplastic materials of the golf ball to result indesirable relationships between the specific gravities of the differentlayers. The core layer and the core center have a difference in specificgravity difference of at least about 0.1 g/cm³. In various embodiments,the specific gravity of the core layer is at least about 0.1 g/cm³greater than the specific gravity of the core center, while in otherembodiments the specific gravity of the core center is at least about0.1 g/cm³ greater than the specific gravity of the core layer. Theserelationships may be obtained by including a heavy-weight filler, ormore of a heavy-weight filler, in the thermoplastic material to attain ahigher specific gravity. Alternatively or additionally, a light-weightfiller or no filler may be included to attain a lower specific gravity.

The cover may be formulated with a pigment, such as a yellow or whitepigment, and in particular a white pigment such as titanium dioxide orzinc oxide. Generally titanium dioxide is used as a white pigment, forexample in amounts of from about 0.5 parts by weight or 1 part by weightto about 8 parts by weight or 10 parts by weight based on 100 parts byweight of polymer. In various embodiments, a white-colored cover may betinted with a small amount of blue pigment or brightener.

Customary additives can also be included in the thermoplastic materials,for example dispersants, antioxidants such as phenols, phosphites, andhydrazides, processing aids, surfactants, stabilizers, and so on. Thecover may also contain additives such as hindered amine lightstabilizers such as piperidines and oxanalides, ultraviolet lightabsorbers such as benzotriazoles, triazines, and hindered phenols,fluorescent materials and fluorescent brighteners, dyes such as bluedye, and antistatic agents.

In various embodiments, one of the first and second thermoplasticmaterials has a flexural modulus of up to about 15,000 psi, preferablyfrom about 8,000 psi to about 15,000 psi, while the other of the firstand second thermoplastic materials has a flexural modulus from about4000 psi up to about 9700 psi. Nonlimiting examples of thermoplasticpolymers that may be used that have a flexural modulus up to about15,000 are the grades of ionomer resins sold by DuPont Company,Wilmington Del. under the name Surlyn® 6320, 8020, 8120, 8320, 9020,9320, and 9320W, and DuPont's HPF2000 and HPF AD1035 ionomer resins;

polyolefin elastomers such as Engage™ 8180; thermoplastic polyesterpolyurethanes and thermoplastic polyether polyurethanes, includingG35D5ON and G38D5ON, sold by Hwa Pao Resins Chemical Co. Ltd. Thethermoplastic polymers may be mixed with an amount of filler or otherpolymers that results in the flexural modulus of the thermoplasticmaterial being up to the desired value. In certain preferred embodimentsthe flexural modulus of the core center is greater than the flexuralmodulus of the core layer.

The core layer may have a thickness of at least about 4 mm or at leastabout 5 mm. The core layer may be up to about 10 mm or up to about 9 mmor up to about 8 mm or up to about 7 mm thick. In certain embodiments,the golf ball has a second core layer between the core layer and thecover. The second core layer includes a fourth thermoplastic materialwith a fourth flexural modulus of from about 30,000 psi to about 120,000psi and that is greater than the flexural modulus of the core layer.Preferably the fourth flexural modulus is from about 40,000 psi or fromabout 50,000 psi or from about 60,000 psi to about 115,000 psi or toabout 110,000 psi or to about 100,000 psi to or to about 90,000 psi.Nonlimiting examples of thermoplastic polymers that may be used are thegrades of ionomer resins sold by DuPont Company, Wilmington DE under thename Surlyn® 6910, 9910, 8920, 7930, 7940, 8940, 8941, 9945, 8945, 9950,9520, 9721, 6120, 8140, 8150, 9120, 9150, 8527, 8528, 9650, and 8660,and DuPont's HPF1000. In particular embodiments, the fourth flexuralmodulus of the second core layer is at least three times the secondflexural modulus of the core layer and at least 30 times the thirdflexural modulus of the cover.

The thermoplastic materials may be made by conventional methods, such asmelt mixing in a single- or twin-screw extruder, a Banbury mixer, aninternal mixer, a two-roll mill, or a ribbon mixer. The firstthermoplastic material is formed into a core center and the secondthermoplastic material is formed into a core layer around the corecenter by usual methods, for example by injection molding with a moldtemperature in the range of 150° C. to 230° C. If there is a second corelayer, the fourth thermoplastic material may be formed in a layer overthe core layer by the same methods. The molded core including corecenter, core layer, and optionally second core layer or further corelayers, may be ground to a desired diameter of from 21 mm to 29 mm aftercooling. Grinding can also be used to remove flash, pin marks, and gatemarks due to the molding process.

A cover layer is molded over the core. In various embodiments, the thirdthermoplastic material used to make the cover may preferably include oneor more of thermoplastic polyurethane elastomers, thermoplastic polyureaelastomers, and the metal cation salts of copolymers of ethylene withethylenically unsaturated carboxylic acids.

The cover may be formed on the multi-layer core by injection molding,compression molding, casting, and so on. For example, when the cover isformed by injection molding, a core fabricated beforehand may be setinside a mold, and the cover material may be injected into the mold. Thecover is typically molded on the core by injection molding orcompression molding. Alternatively, another method that may be usedinvolves pre-molding a pair of half-covers from the cover material bydie casting or another molding method, enclosing the core in thehalf-covers, and compression molding at, for example, between 120° C.and 170° C. for a period of 1 to 5 minutes to attach the cover halvesaround the core. The core may be surface-treated before the cover isformed over it to increase the adhesion between the core and the cover.Nonlimiting examples of suitable surface preparations include mechanicalor chemical abrasion, corona discharge, plasma treatment, or applicationof an adhesion promoter such as a silane or of an adhesive. The covertypically has a dimple pattern and profile to provide desirableaerodynamic characteristics to the golf ball.

Typically, the cover may have a thickness of from about 0.5 mm to about4 mm. If there are two cover layers, typically, the cover layers mayeach independently have a thickness of from about 0.3 mm to about 2.0mm, preferably from about 0.8 mm to about 1.6 mm.

The golf balls can be of any size, although the USGA requires that golfballs used in competition have a diameter of at least 1.68 inches(42.672 mm) and a weight of no greater than 1.62 ounces (45.926 g). Forplay outside of USGA competition, the golf balls can have smallerdiameters and be heavier.

After a golf ball has been molded, it may undergo various furtherprocessing steps such as buffing, painting and marking. In aparticularly preferred embodiment of the invention, the golf ball has adimple pattern that coverage of 65% or more of the surface. The golfball typically is coated with a durable, abrasion—resistant andrelatively non-yellowing finish coat.

The description is merely exemplary in nature and, thus, variations thatdo not depart from the gist of the disclosure are a part of theinvention. Variations are not to be regarded as a departure from thespirit and scope of the disclosure

What is claimed is:
 1. A golf ball, comprising: a core center having adiameter from about 21 mm to about 29 mm and comprising a firstthermoplastic material having a first flexural modulus of up to about15,000 psi; a core layer disposed radially outward from the core center,wherein the core layer has a thickness of at least about 4 mm andcomprises a second thermoplastic material having a second flexuralmodulus of up to about 9700 psi; and a cover disposed radially outwardfrom the core layer, wherein the cover comprises a third thermoplasticmaterial having a third flexural modulus of up to about 6,000 psi;wherein the first flexural modulus is greater than the second flexuralmodulus, the second flexural modulus is greater than the third flexuralmodulus, and the specific gravity of the core layer and the specificgravity of the core center differ by at least about 0.1 g/cm³.
 2. A golfball according to claim 1, wherein the third flexural modulus is up toabout 5,000 psi.
 3. A golf ball according to claim 1, wherein thespecific gravity of the core layer is at least about 0.1 g/cm³ greaterthan the specific gravity of the core center.
 4. A golf ball accordingto claim 1, wherein the specific gravity of the core center is at leastabout 0.1 g/cm³ greater than the specific gravity of the core layer.5-8. (canceled)
 9. A golf ball, comprising: a core center having adiameter from about 21 mm to about 29 mm and comprising a firstthermoplastic material comprising an ionomer resin and a polyolefinelastomer and having a 10-130 kg compression deformation of at leastabout 4 mm and a first flexural modulus of up to about 9700 psi; a corelayer disposed radially outward from the core center, wherein the corelayer has a thickness of at least about 5 mm and comprises a secondthermoplastic material having a second flexural modulus of up to about15,000 psi; and a cover disposed radially outward from the core layer,wherein the cover comprises a third thermoplastic material having athird flexural modulus of up to about 5,000 psi; wherein the secondflexural modulus is greater than the first flexural modulus, the secondflexural modulus is at least about 10,000 psi greater than the thirdflexural modulus, and the specific gravity of the core layer and thespecific gravity of the core center differ by at least about 0.1 g/cm³.10. A golf ball according to claim 9, wherein the specific gravity ofthe core layer is at least about 0.1 g/cm³ greater than the specificgravity of the core center.
 11. A golf ball according to claim 9,wherein the specific gravity of the core center is at least about 0.1g/cm³ greater than the specific gravity of the core layer.
 12. A golfball according to claim 9, any one of claim 9, wherein the thirdflexural modulus is up to about 2,000 psi. 13-15. (canceled)